JP2002114981A - Flame-retardant, flame-retardant resin composition and flame-retardant resin molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant which has such advantages that it contains no halogen and has a high melting point and low volatility and, simultaneously, it does not reduce the inherent properties of resins. SOLUTION: The flame-retardant is composed of at least one phosphazene compound selected from the group consisting of a cyclic phosphazene compound to be represented by formula (3) (wherein (m) is an integer of 3-25; R1 is a cyano-substituted phenyl group; R2 is a 1-18C alkyl or the like, and when R2 is two or more, R2 may be the same or different; (p) and (q) are each a real number and meet p>0, q>=0, and p+q=2) and a straight chain phosphazene compound to be represented by formula (4) (wherein R1, R2, (p) and (q) are the same as defined above; (n) is an integer of 3-1,000; X' is a group of -P(OR1)4 or the like; Y' is a group of -N=P(OR1)3 or the like).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a flame retardant, a flame retardant resin composition and a flame retardant resin molded product.

[0002]

[0003] Plastics are used in applications such as electric and electronic products, OA equipment, office equipment, and communication equipment because of their excellent moldability, mechanical properties, and appearance. . In these applications, it is necessary to make the resin flame-retardant due to problems such as heat generation and ignition of internal components.

[0003] In order to impart flame retardancy to a thermoplastic resin or a thermosetting resin, it is common to add a flame retardant before molding the resin. As the flame retardant, inorganic hydroxides, organic phosphorus compounds, organic halogen compounds, halogen-containing organic phosphorus compounds and the like are known.

[0004] Among these, the flame retardant with excellent flame retardant effect is
Halogen-containing compounds such as organic halogen compounds and halogen-containing organic phosphorus compounds.

[0005] However, these halogen-containing compounds are thermally decomposed during resin molding to generate hydrogen halide,
Causes mold corrosion, resin degradation and coloration. Further, when the resin is burned due to a fire or the like, there is a problem that harmful gas or smoke is generated for living things such as hydrogen halide.

On the other hand, halogen-free flame retardants are inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide and organic phosphorus compounds.

However, inorganic hydroxides exhibit flame retardancy due to water generated by thermal decomposition, and therefore have a low flame retardant effect.
Therefore, it must be added in a large amount, but there is a disadvantage in that the addition of a large amount impairs the inherent properties of the resin.

[0008] Organic phosphorus compounds are widely used because of their relatively good flame-retardant effects. Representative examples thereof include triphenyl phosphate (TPP) and tricresyl phosphate (TCP). Are known. However, since these organic phosphorus compounds are liquids or low-melting-point solids, they have high volatility and have problems such as lowering the molding temperature of the resin, blocking and bleeding (juicing) during kneading.

Furthermore, the resin compositions containing these organic phosphorus compounds have the disadvantage that dripping (dipping of molten resin) and fire spread due to the dripping occur during combustion.
Therefore, an organic phosphorus compound is added to a resin, and the flame retardancy test UL-94 (Testing for Flammability of Plastics, which is a standard for evaluating flame retardancy) is used as a standard.
Plastic MaterialS for Parts in Devices & Applianc
es), in order to achieve “Evaluation V-0 (combustion does not continue for a certain period of time, ignites cotton, and there is no molten dripping)”, for example, as an agent for preventing molten resin from dripping during combustion, for example, poly It is necessary to add a fluorine resin such as tetrafluoroethylene resin (PTFE). However, as described above, these fluororesins contain a halogen element and generate toxic gases to the human body when burned.

Therefore, it does not contain halogen, has a high melting point, has low volatility, and does not deteriorate the inherent properties of the resin such as mechanical properties and moldability, and has no problems such as blocking or bleeding during kneading. It is desired to develop a new flame retardant that does not cause dripping during combustion.

[0011]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a specific partially crosslinked phenoxyphosphazene compound can be a desired flame retardant. The present invention has been completed based on such findings.

According to the present invention, general formula (1)

[0013]

Embedded image

[Wherein m represents an integer of 3 to 25]. Ph represents a phenyl group. A phosphazene compound represented by the general formula (2):

[0015]

Embedded image

Wherein X represents a group -N = P (OPh) ₃ or a group -N = P (O) OPh, and Y represents a group -P (OPh) _4.
Or a group -P (O) (OPh) ₂ . n is 3 to 100
Indicates an integer of 0. Ph is the same as above. At least one phosphazene compound selected from the group consisting of linear phosphazene compounds represented by the formula: is an o-, m-, p-phenylene group, a biphenylene group and a group

[0017]

Embedded image

Wherein A is —C (CH ₃ ) ₂ —, —SO
_{It represents 2-} , -S- or -O-. A compound cross-linked by at least one kind of cross-linking group selected from the group consisting of: a cross-linking group interposed between two oxygen atoms from which the phenyl group of the phosphazene compound has been eliminated; Wherein the content of phenyl groups in the crosslinked compound is 50 to 99.9% based on the total number of all phenyl groups in the phosphazene compound (1) and / or (2). Flame retardant (hereinafter,
This flame retardant is referred to as “flame retardant A”).

The flame retardant A comprising the crosslinked phenoxyphosphazene compound of the present invention does not contain a halogen, and therefore thermally decomposes at the time of molding the resin to generate hydrogen halide, causing corrosion of a mold, deterioration and coloring of the resin. In addition, when the resin burns due to a fire or the like, no harmful gas such as hydrogen halide or smoke is generated. The crosslinked phenoxyphosphazene compound of the present invention has low volatility, does not lower the molding temperature of the resin, and causes problems such as blocking and bleeding (juicing) during kneading and dripping during combustion. There is no. In addition, mechanical properties such as impact resistance, heat resistance,
It does not lower the inherent properties of the resin such as moldability.

Further, according to the present invention, (a) a flame-retardant resin composition comprising 0.1 to 100 parts by weight of a flame retardant A per 100 parts by weight of a thermoplastic resin or a thermosetting resin;
(B) a flame-retardant resin composition comprising 0.1 to 100 parts by weight of a flame retardant A and 0.01 to 50 parts by weight of an inorganic filler with respect to 100 parts by weight of a thermoplastic resin or a thermosetting resin;
(C) A flame-retardant resin composition comprising 0.1 to 50 parts by weight of a flame retardant A and 0.1 to 50 parts by weight of a halogen-free organic phosphorus compound per 100 parts by weight of a thermoplastic resin or a thermosetting resin. And (d) a flame retardant resin composition comprising 0.1 to 100 parts by weight of a flame retardant A and 0.01 to 2.5 parts by weight of a fluororesin per 100 parts by weight of a thermoplastic resin.

According to the present invention, the above (a) to
A flame-retardant resin molded article obtainable by molding the flame-retardant resin composition (d) is provided.

Further, at least one selected from the group consisting of the cyclic phosphazene compound represented by the general formula (1) and the linear phosphazene compound represented by the general formula (2)
It has also been found that the desired effects of the present invention as described above are exhibited when a kind of phosphazene compound is used in combination with an inorganic phosphorus compound or an organic phosphorus compound containing no halogen.

According to the present invention, at least one phosphazene compound selected from the group consisting of a cyclic phosphazene compound represented by the general formula (1) and a linear phosphazene compound represented by the general formula (2) Flame retardant (hereinafter,
This flame retardant is referred to as “flame retardant B”).

According to the present invention, (e) 100 parts by weight of a thermoplastic resin or a thermosetting resin is added to the flame retardant B0.
A flame retardant resin composition containing 1 to 100 parts by weight and an inorganic filler of 0.01 to 50 parts by weight; and (f) 100 parts by weight of a thermoplastic resin or a thermosetting resin, a flame retardant B
The present invention provides a flame-retardant resin composition containing 0.1 to 50 parts by weight and 0.1 to 50 parts by weight of a halogen-free organic phosphorus compound.

Further, according to the present invention, the above (e) to (e)
A flame-retardant resin molded article obtainable by molding the flame-retardant resin composition (f) is provided.

Further, at least one selected from the group consisting of a cyclic phosphazene compound represented by the following formula (3) and a linear phosphazene compound represented by the following formula (4):
It has been found that the desired effects of the present invention as described above are exhibited also when using a kind of phosphazene compound as a flame retardant.

According to the present invention, general formula (3)

[0028]

Embedded image

Wherein m is the same as above. R ¹ represents a cyano-substituted phenyl group. R ² is an alkyl group having 1 to 18 carbon atoms,

[0030]

Embedded image

Or group

[0032]

Embedded image

Is shown. Here, R ³ represents a hydrogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, an allyl group or a phenyl group. If the R ² there are two or more, R ² may be the same or different. p and q are p
> 0, q ≧ 0, and is a real number satisfying p + q = 2. A cyclic phosphazene compound represented by the general formula (4):

[0034]

Embedded image

Wherein n, R ¹ , R ² , p and q are as defined above. X ′ is a group —P (OR ¹ ) ₄ , a group —P (OR ¹ ) ₃ (OR
² ) group, -P (OR ¹ ) ₂ (OR ² ) ₂ , group -P (OR ¹ )
(OR ² ) ₃ , group —P (OR ² ) ₄ , group —P (O) (O
R ¹ ) ₂ , group —P (O) (OR ¹ ) (OR ² ) or group —P
(O) (OR ² ) ₂ , wherein Y ′ is a group —N ＝ P (O
R ¹ ) ₃ , group -N = P (OR ¹ ) ₂ (OR ² ), group -N = P
(OR ¹ ) (OR ² ) ₂ , group -N = P (OR ² ) ₃ , group -N
= Indicates a P (O) OR ¹ or a group ^{-N = P (O) OR 2} . ]
And a flame retardant comprising at least one phosphazene compound selected from the group consisting of linear phosphazene compounds represented by the formula (hereinafter, this flame retardant is referred to as "flame retardant C").

According to the present invention, the flame retardant C is 0.1 to 1 per 100 parts by weight of the thermoplastic resin or the thermosetting resin.
A flame retardant resin composition containing 00 parts by weight is provided.

Further, according to the present invention, there is provided a flame-retardant resin molded article obtainable by molding the above-mentioned flame-retardant resin composition.

[0038]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Flame retardant (a) Flame retardant A First, the flame retardant A will be described.

The crosslinked phenoxyphosphazene compound of the present invention can be obtained by adding an alkali metal salt of phenol and an alkali metal salt of an aromatic dihydroxy compound to a dichlorophosphazene oligomer (a mixture of a cyclic dichlorophosphazene oligomer and a linear dichlorophosphazene oligomer). It can be produced by reacting a salt. As the dichlorophosphazene oligomer, a cyclic dichlorophosphazene oligomer and a linear dichlorophosphazene oligomer may be separated and used alone. Alkali metal salt of phenol and alkali metal salt of aromatic dihydroxy compound,
These may be mixed and provided for the reaction, or the alkali metal salt of phenol may be reacted, and further the alkali metal salt of an aromatic dihydroxy compound may be reacted, or vice versa.

Dichlorophosphazene oligomers are disclosed in JP-A-57-87427, JP-B-58-19604, JP-B-61-1363, and JP-B-62-20.
It can be produced according to a known method such as that disclosed in JP-A-124. As an example, first, ammonium chloride and phosphorus pentachloride (or ammonium chloride, phosphorus trichloride, and chlorine) may be reacted with chlorobenzene as a solvent at about 120 to 130 ° C. for dehydrochlorination.

Examples of the alkali metal salt of phenol include phenol Na salt, K salt and Li salt. Further, as an alkali metal salt of an aromatic dihydroxy compound,
Having one or more benzene rings in the molecule and
Any known alkali metal salt having a hydroxy group can be used. For example, resorcinol, hydroquinone, catechol, 4,4′-isopropylidenediphenol (bisphenol-A), 4,4′-sulfonyldiphenol ( Bisphenol-S), 4,4'-
Thiodiphenol, 4,4′-oxydiphenol,
Examples thereof include alkali metal salts such as 4,4'-diphenol. The alkali metal salt is not particularly limited, but a Li salt is preferred. As the alkali metal salt of the aromatic dihydroxy compound, one kind can be used alone, or two or more kinds can be used in combination.

The use amount of the alkali metal salt of phenol and the alkali metal salt of the aromatic dihydroxy compound with respect to the dichlorophosphazene oligomer is usually about 1 to 1.5 equivalents (total amount of both alkali metal salts). Chlorine based), preferably 1 to
It may be about 1.2 equivalents (based on the amount of chlorine).
The use ratio of the two alkali metal salts (alkali metal salt of aromatic dihydroxy compound / alkali metal salt of phenol, molar ratio) is not particularly limited and can be appropriately selected from a wide range, but is usually about 1/2000 to 1/4. And it is sufficient.
Within this range, the desired crosslinked phenoxyphosphazene compound of the present invention can be obtained.

When the use ratio is significantly smaller than 1/2000, the effect of the cross-linking compound is reduced, and it may be difficult to solve the above-mentioned problems such as prevention of dripping of the melt. On the other hand, when the use ratio is much larger than 1/4, the crosslinking proceeds excessively, and the obtained crosslinked phenoxyphosphazene compound becomes insoluble and infusible, and there is a possibility that the dispersibility in the resin may be reduced.

The reaction between the dichlorophosphazene oligomer and both alkali metal salts is usually carried out at a temperature of about room temperature to about 150 ° C., such as aromatic hydrocarbons such as toluene and halogenated aromatic hydrocarbons such as chlorobenzene. Performed in a solvent.

The terminal groups X and Y in the above general formula (2) vary depending on the reaction conditions and the like. When a mild reaction is carried out under ordinary reaction conditions, for example, in a non-aqueous system, X becomes -N = P
(OPh) ₃ , Y has a structure of —P (OPh) ₄ , and the reaction is carried out under reaction conditions in which moisture or an alkali metal hydroxide is present in the reaction system or under severe reaction conditions in which a transfer reaction occurs. If performed, X is -N = P (OPh)
₃ , in addition to the structure where Y is -P (OPh) ₄ , X is -N = P
(O) OPh and Y having a structure of -P (O) (OPh) ₂ are mixed.

Thus, the crosslinked phenoxyphosphazene compound of the present invention is produced. The decomposition temperature of the crosslinked phenoxyphosphazene compound of the present invention is generally from 250 to 350 ° C.
Within the range.

In the above method, when the dichlorophosphazene oligomer is reacted with only an alkali metal salt of phenol without using an alkali metal salt of an aromatic dihydroxy compound, a cyclic compound represented by the general formula (1) is obtained. A phosphazene compound or a linear phosphazene compound represented by the general formula (2) is produced. However, when an alkali metal salt of an aromatic dihydroxy compound is used together with an alkali metal salt of phenol, the cyclic phosphazene compound represented by the general formula (1) or the linear phosphazene compound represented by the general formula (2) can be used. The phenoxyphosphazene compound of the present invention in which a part of the phenyl group is replaced by a crosslinking group is produced.

The content of phenyl groups in the crosslinked phenoxyphosphazene compound of the present invention is 50 to 99.9% based on the total number of all phenyl groups in the phosphazene compounds (1) and / or (2). Preferably 70-90%
It is.

The crosslinked phenoxyphosphazene compound of the present invention obtained above is isolated and purified from the reaction mixture according to a conventional isolation method, for example, a conventionally known method such as washing, filtration and drying.

(B) Flame retardant B Next, the flame retardant B will be described.

The cyclic phosphazene compound represented by the general formula (1) and the linear phosphazene compound represented by the general formula (2) are both known compounds. These phosphazene compounds are described, for example, in James E. Mark, Harry R. A.
"Inorganic Polymers" Pret by llcock, Robert West
ice-Hall International, Inc., 1992, p61-p140.

The cyclic phosphazene compound represented by the general formula (1) and the linear phosphazene compound represented by the general formula (2) are used, for example, in the production of the above-mentioned crosslinked phenoxyphosphazene compound. It is produced by the same method as described above except that no metal salt is used.

The phosphazene compound obtained above is isolated and purified from the reaction mixture according to a conventional isolation method, for example, a conventionally known method such as washing, filtration and drying.

Specific examples of the cyclic phosphazene compound represented by the general formula (1) include hexachlorocyclotriphosphazene and octachlor obtained by reacting ammonium chloride and phosphorus pentachloride at 120 to 130 ° C. Cyclic and linear n such as cyclotetraphosphazene is 3
A phosphazene compound in which a phenoxy group is substituted for a chlorphosphazene mixture represented by an integer of from 25 to 25, and a single substance such as hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, or decachlorocyclopentaphosphazene is taken out from the chlorphosphazene mixture, Cyclic phosphazene compounds such as hexaphenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, decafenoxycyclopentaphosphazene and the like in which a single substance is substituted with a phenoxy group are exemplified. Further, when the linear phosphazene compound represented by the general formula (2) is specifically exemplified, for example, hexachlorocyclotriphosphazene is heated to 220 to 250 ° C., and n obtained by ring-opening polymerization is 3 to 1000. And a linear phosphazene compound in which dichlorophosphazene represented by the following formula is substituted by a phenoxy group.

Among these, cyclic and linear n is 3
A phosphazene compound in which a phenoxy group is substituted for a chlorphosphazene mixture represented by an integer of from 25 to 25 is preferable.

(C) Flame Retardant C Next, the flame retardant C will be described.

As the phosphazene compound represented by the general formula (3), for example, R ¹ is a cyano-substituted phenyl group, R ²
Is an alkyl group having 1 to 8 carbon atoms,

[0058]

Embedded image

Or a group

[0060]

Embedded image

Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an allyl group, p is 0.3 to 1.7,
A cyclic phosphazene compound in which q is 0.3 to 0.7 is preferred.

Further, as the phosphazene compound represented by the general formula (4), for example, R ¹ is a cyano-substituted phenyl group, R ² is an alkyl group having 1 to 8 carbon atoms,

[0063]

Embedded image

Or a group

[0065]

Embedded image

Wherein R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an allyl group, p is 0.3 to 1.7,
Linear phosphazene compounds wherein q is from 0.3 to 0.7 are preferred.

Examples of the cyano-substituted phenyl represented by R ¹ include 2-cyanophenyl, 3-cyanophenyl,
4-cyanophenyl group and the like.

More specifically, examples of the phosphazene compound represented by the general formula (3) or (4) include, for example, cyclotriphosphazene, cyclotetraphosphazene, cyclopentaphosphazene and the like in which a cyanophenoxy group and a phenoxy group are mixed and substituted. Cyclic phosphazene compound or linear phosphazene compound.

Specific examples of the cyclic phosphazene compound in which a cyanophenoxy group and a phenoxy group are mixed and substituted are as follows:
For example, cyclotrienes such as monocyanophenoxypentaphenoxycyclotriphosphazene, dicyanophenoxytetraphenoxycyclotriphosphazene, tricyanophenoxytriphenoxycyclotriphosphazene, tetracyanophenoxydiphenoxycyclotriphosphazene, and pentacyanophenoxymonophenoxycyclotriphosphazene. Phosphazene compounds, monocyanophenoxypeptaphenoxycyclotetraphosphazene,
Dicyanophenoxyhexaphenoxycyclotetraphosphazene, tricyanophenoxypentaphenoxycyclotetraphosphazene, tetracyanophenoxytetraphenoxycyclotetraphosphazene, pentacyanophenoxytriphenoxycyclotetraphosphazene, hexacyanophenoxydiphenoxycyclotetraphosphazene, and heptacyanophenoxymonophenoxy Examples include cyclotetraphosphazene such as cyclotetraphosphazene, and cyclic phosphazene compounds such as cyclopentaphosphazene compound in which cyanophenoxy and phenoxy groups are mixed and substituted.

The linear phosphazene compound includes, for example, a linear phosphazene compound in which a cyanophenoxy group and a phenoxy group are mixed and substituted.

These phosphazene compounds may be used alone or as a mixture of two or more.

Among the above phosphazene compounds, phosphazene oligomers (mixtures of cyclic and linear products) in which a cyanophenoxy group and a phenoxy group are mixed and substituted are preferred from the viewpoint of the production method, availability, and the like. When the content ratio of cyanophenoxy groups to phenoxy groups is 1: 7 to 7: 1
The phosphazene oligomer is particularly preferred.

The phosphazene compound having a cyanophenoxy group (phosphazene compound represented by formula (3) or (4)) of the present invention can be produced by various methods.

As a raw material for producing a phosphazene compound having a cyanophenoxy group, for example, as shown in the following reaction formula-1, ammonium chloride and phosphorus pentachloride are used.
Cyclic and linear phosphazene compounds such as hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene obtained by reacting at ~ 130 ° C can be used. In this reaction, a solvent such as tetrachloroethane or chlorobenzene can be used as a solvent. Reaction formula-1

[0075]

Embedded image

Further, as the above-mentioned production raw material, the above-mentioned reaction formula
Hexachlorocyclotriphosphazene was extracted from the cyclic and linear mixture obtained by the method shown in 1 and
Dichlorophosphazene obtained by heating to 20 to 250 ° C. and performing ring-opening polymerization can be used as a linear phosphazene compound (see the following reaction formula-2). Reaction formula-2

[0077]

Embedded image

The method for producing a phosphazene compound having a cyanophenoxy group according to the present invention includes, for example, an alkali metal salt of cyanophenol and phenol (aroma) mixed with the cyclic or linear phosphazene compound obtained above in a desired ratio. A phenol substituted with an alkyl group having 1 to 10 carbon atoms, an allyl group and a phenyl group on the ring, and a naphthol (an alkyl group having 1 to 10 carbon atoms, an allyl group and a phenyl group are substituted on the aromatic ring) Including naphthol)
And a method of reacting with a mixture with at least one kind of alkali metal salt selected from the group consisting of alcohols having 1 to 18 carbon atoms (hereinafter, these are referred to as "phenols").

For example, a dehydration reaction is carried out from a mixture of cyanophenol and phenols mixed in a desired ratio with sodium hydroxide to prepare a sodium salt of cyanophenol and a sodium salt of phenols. In this dehydration reaction, water may be simply removed, and a solvent may or may not be used. When a solvent is used, benzene, toluene, xylene, chlorobenzene, and the like are selected, and azeotropic distillation with the solvent may increase the dehydration efficiency. Next, after adding the cyclic or linear phosphazene compound obtained above to the sodium salt of cyanophenol and the sodium salt of phenols, 50 to 150
By heating at 1 ° C. for 1 to 24 hours to perform a substitution reaction, a phosphazene compound having an intended cyanophenoxy group can be obtained. Reaction formula-3

[0080]

Embedded image

The desired phosphazene compound having a cyanophenoxy group can be produced from the dehydration reaction and the substitution reaction as described above. Considering the efficiency of each operation, chlorobenzene is selected as the solvent. When chlorobenzene is used as a solvent, the substitution reaction is completed when the chlorbenzene is refluxed for about 12 hours.

Further, as a production method other than those described above, a method of reacting an alkali metal salt of cyanophenol and an alkali metal salt of phenol with a separated or purified cyclic or linear dichlorophosphazene, or a method for preparing dichlorophosphazene oligomers A method in which an alkali metal of cyanophenol is reacted, and then an alkali metal salt of phenols is successively reacted.

The phosphazene compound having a cyanophenoxy group obtained above is isolated and purified from the reaction mixture according to a conventional isolation method, for example, a conventionally known method such as washing, filtration and drying.

Flame Retardant Resin Composition The flame retardant resin composition of the present invention is obtained by blending the above flame retardant A, B or C with a thermoplastic resin or a thermosetting resin. Hereinafter, unless otherwise specified, the flame-retardant resin composition of the present invention is a general term for a resin composition having any one of a thermoplastic resin and a thermosetting resin as a matrix.

(A) Thermoplastic resin As the thermoplastic resin used in the present invention, conventionally known thermoplastic resins can be widely used, and examples thereof include polyethylene, polypropylene, polyisoprene, polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polybutadiene, Styrene resin, impact-resistant polystyrene, acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin),
Methyl methacrylate-butadiene-styrene resin (M
BS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acrylic rubber-styrene resin (AAS resin), polymethyl (meth) acrylate, polycarbonate, modified polyphenylene ether (PPE), polyamide, polyphenylene sulfide, Polyimide, polyetheretherketone, polysulfone, polyarylate, polyetherketone, polyethernitrile, polythioethersulfone, polyethersulfone, polybenzimidazole, polycarbodiimide, polyamideimide, polyetherimide, liquid crystal polymer, composite plastic, etc. Can be

Among these thermoplastic resins, polyester, ABS resin, polycarbonate, modified polyphenylene ether, polyamide and the like can be preferably used.

In the present invention, the thermoplastic resins are used alone or as a mixture of two or more.

(B) Thermosetting Resin As the thermosetting resin, conventionally known thermosetting resins can be widely used, and polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, epoxy resin Resins and the like can be mentioned.

Among these thermosetting resins, polyurethane, phenol resin, melamine resin, epoxy resin and the like can be particularly preferably used.

The epoxy resin is not particularly limited, and those conventionally known can be widely used.
As an example, bisphenol-A type epoxy resin,
Bisphenol-F type epoxy resin, bisphenol-
AD epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, cycloaliphatic epoxy resin, glycidyl ester resin, glycidylamine epoxy resin, heterocyclic epoxy resin, urethane-modified epoxy resin, brominated bisphenol-A Type epoxy resin and the like.

In the present invention, one type of thermosetting resin is used alone, or two or more types are mixed.

The mixing ratio of the flame retardant A, the flame retardant B or the flame retardant C to the thermoplastic resin or the thermosetting resin is not particularly limited. 0.1-100 per part by weight
Parts by weight, preferably 1 to 50 parts by weight, more preferably 5 parts by weight.
The content is preferably up to 30 parts by weight.

(C) Inorganic filler An inorganic filler can be added to the flame-retardant resin composition of the present invention in order to further improve the anti-dripping property.

Heretofore, these inorganic fillers have been mainly used as a reinforcing material for improving the mechanical properties of the resin. However, the present inventor, by coexisting the above-mentioned flame retardant and the inorganic filler in the resin, they act synergistically, not only the improvement of mechanical properties, but also the flame retardant effect of the above-mentioned flame retardant, especially It has been found that the anti-dripping effect is significantly improved.

When the flame retardant and the inorganic filler coexist in the resin, the resin surface layer becomes dense and strong, suppressing the diffusion of generated gas on the resin surface during combustion, and furthermore, the carbon layer of the flame retardant. It is thought that by promoting the formation of (char), an excellent flame retardant effect is exhibited. In particular, in the case of the flame retardant B, it is essential to use it together with the inorganic filler.

As the inorganic filler, known resin fillers can be used. For example, mica, kaolin, talc, silica, clay, barium sulfate, barium carbonate, calcium carbonate, calcium sulfate, calcium silicate, titanium oxide,
Glass beads, glass balloons, glass flakes, glass fibers, fibrous alkali metal titanate (potassium titanate fiber, etc.), fibrous transition metal salt (aluminum borate fiber, etc.), fibrous alkaline earth metal borate (Magnesium borate fiber, etc.), zinc oxide whisker, titanium oxide whisker, magnesium oxide whisker, gypsum whisker, aluminum silicate (mineral name mullite) whisker, calcium silicate (mineral name wollastonite) whisker, silicon carbide whisker, titanium carbide whisker , Silicon nitride whisker, titanium nitride whisker, carbon fiber, alumina fiber, alumina-silica fiber, zirconia fiber,
Quartz fiber and the like can be mentioned.

Among these inorganic fillers, fibrous alkali metal titanate, fibrous transition metal borate salt, fibrous alkaline earth metal borate salt, zinc oxide whisker, titanium oxide whisker, magnesium oxide whisker, aluminum silicate whisker Calcium silicate whiskers, silicon carbide whiskers, titanium carbide whiskers, silicon nitride whiskers, titanium nitride whiskers and the like, and those having shape anisotropy such as mica are preferable, and fibrous alkali metal titanate and fibrous boric acid are preferable. Transition metal salts, fibrous alkaline earth metal borate salts, titanium oxide whiskers, calcium silicate whiskers and the like are particularly preferred.

One of these inorganic fillers can be used alone, or two or more can be used in combination.

Among these inorganic fillers, those having shape anisotropy such as whiskers and mica can be preferably used.

The potassium titanate fiber which is one of the inorganic fillers usually has an average fiber diameter of 0.05 to 2.0.
Potassium hexatitanate fibers having an average fiber length of about 1 µm and an average fiber length of about 1 to 500 µm, and preferably having an aspect ratio (fiber length / fiber diameter) of 10 or more can be given. Among these, potassium hexatitanate fibers having a pH of 6.0 to 8.5 are particularly preferred. Here, the pH of the potassium titanate fiber
The term “pH” refers to a pH value measured at 20 ° C. after stirring a 1.0% by weight suspension of potassium titanate fiber (using deionized water) for 10 minutes. If the pH of the potassium titanate fiber greatly exceeds 8.5, the physical properties of the resin and the heat discoloration resistance may decrease, which is not preferable. On the other hand, when the pH is 6.0
If the value is extremely below, not only the effect of improving the strength of the obtained resin composition is reduced, but also the residual acid may cause corrosion of the processing machine and the mold, which is not preferable.

The mixing ratio of the inorganic filler to the thermoplastic resin or the thermosetting resin is not particularly limited. However, in consideration of the balance between the improvement of the mechanical properties and the improvement of the flame-retardant performance, the mixing ratio of the thermoplastic resin is usually higher than that of the thermoplastic resin. Resin or thermosetting resin 1
0.01 to 50 parts by weight, preferably 1 to 100 parts by weight
It is preferable to use up to 20 parts by weight.

(D) Organophosphorus Compound Containing No Halogen In order to further improve the flame retardancy of the flame retardant resin composition of the present invention, an organophosphorus compound containing no halogen (hereinafter referred to as “halogen-free organic compound”) is used. Phosphorus compound).

It is conventionally known that halogen-free organic phosphorus compounds improve the flame retardancy of a matrix such as a resin. However, the present inventor, when a specific phosphazene compound used in the present invention and a halogen-free organic phosphorus compound are used in combination, a synergistic effect is exhibited,
It has been found that the flame retardant effect can be significantly enhanced. Although the reason why such a remarkable effect is achieved is not yet sufficiently clear, the combined use of the two forms a carbonized layer on the surface of the resin composition, forms an expanded layer, and decomposes both layers during combustion. This is probably because the diffusion and heat transfer of the product were suppressed.

As the halogen-free organic phosphorus compound,
Conventionally known ones can be widely used. For example, Tokiko 6-1
No. 9003, JP-A-2-115262, JP-A-5-1079, JP-A-6-322277, U.S. Pat. No. 5,122,556, and the like.

More specifically, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate, xylyl diphenyl phosphate, tolyl dixylyl phosphate , Tris (norylphenyl) phosphate, phosphate esters such as (2-ethylhexyl) diphenyl phosphate, hydroxyl-containing phosphate esters such as resorcinol diphenyl phosphate, hydroquinone diphenyl phosphate, resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), Bisphenol-A bis (diphenyl phosphate), bisphenol S bis (diphenyl phosphate), resorcinol bis (dicylyl phosphate), hydroquinone bis (dicylyl phosphate), bisphenol-A bis (ditolyl phosphate), biphenol-A bis (dicylyl phosphate), bisphenol-S bis (dixylyl) Phosphate or phosphine oxide compounds such as trilaurylphosphine, triphenylphosphine, tolylphosphine, triphenylphosphine oxide, and tolylphosphine oxide.

Among these halogen-free organic phosphorus compounds, triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), bisphenol-A bis (diphenyl phosphate), resorcinol bis (Dixylyl phosphate), condensed phosphate compounds such as hydroquinone bis (dixylyl phosphate) and bisphenol-A bis (ditolyl phosphate), and phosphine oxide compounds such as triphenylphosphine oxide and tolylphosphine oxide are preferable. Triphenyl phosphate, resorcinol bis (diphenyl phosphate), resorcinol bis (dixylyl phosphate) Triphenylphosphine oxide, and the like are preferable.

As the halogen-free organic phosphorus compound, one type can be used alone, or two or more types can be used in combination.

The halogen-free organic phosphorus compound is particularly effective when used in combination with the flame retardant A or the flame retardant B.

The mixing ratio of the halogen-free organic phosphorus compound to the thermoplastic resin or the thermosetting resin is not particularly limited. The amount is 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, per 100 parts by weight of the thermoplastic resin or the thermosetting resin. In this case, the blending ratio of the flame retardant is usually 0.1 to 50 parts by weight with respect to 100 parts by weight of the thermoplastic resin or the thermosetting resin.
Preferably, it is 5 to 30 parts by weight.

(E) Fluororesin Further, a fluorine resin can be added to the flame-retardant resin composition of the present invention using a thermoplastic resin as a matrix within a range not to impair the object of the present invention. The blending amount is not particularly limited, but the thermoplastic resin 1
The amount is usually 0.01 to 2.5 parts by weight, preferably 0.1 to 1.2 parts by weight, per 100 parts by weight.

As the fluororesin, conventionally known ones can be widely used. For example, polytetrafluoroethylene resin (PTF)
E), ethylene tetrafluoride-propylene hexafluoride copolymer resin (FEP), ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer resin (PFA), ethylene tetrafluoride-ethylene copolymer resin (ETFE), Examples thereof include fluorinated ethylene resin (CTFE) and polyvinylidene fluoride (PVdF), and PTFE is particularly preferable. By the addition of the fluororesin, the drip prevention effect is further exhibited.

It is particularly effective to use the fluororesin in combination with the flame retardant A.

(F) Other additives The flame-retardant resin composition of the present invention exhibits an excellent flame-retardant effect without using a compound containing halogen such as chlorine or bromine as a flame-retardant component. Although it is a resin composition, it is also possible to add a commonly used known flame retardant additive in an appropriate combination as long as the excellent effect is not impaired.

The additive for flame retarding is not particularly limited as long as it exhibits a flame retarding effect.
Metal oxides such as tin oxide, iron oxide, molybdenum oxide, copper oxide and manganese dioxide, aluminum hydroxide, magnesium hydroxide, zirconium hydroxide, aluminum hydroxide treated with oxalic acid, magnesium hydroxide treated with nickel compounds, etc. Metal hydroxide, sodium carbonate, calcium carbonate, barium carbonate, alkali metal salt or alkaline earth metal salt such as sodium alkyl sulfonate, chlorinated paraffin, perchlorocyclopentadecane, tetrabromobisphenol-A, epoxy resin, bis ( Organic chlorine compounds or organic bromine compounds such as tribromophenoxy) ethane and bis (tetrabromophthalimino) ethane;
Antimony compounds such as antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, red phosphorus, halogen-containing phosphate ester compounds, halogen-containing condensed phosphate ester compounds or phosphonate ester compounds, melamine, melamine cyanurate, melamine Nitrogen-containing compounds such as phosphate, melam, melem, melon, succinoguanamine, guanidine sulfamate, ammonium sulfate, ammonium phosphate, ammonium polyphosphate, alkylamine phosphate, and boron compounds such as zinc borate, barium metaborate, and ammonium borate , Silicone polymers, silicon compounds such as silica, and heat-expandable graphite.

One of these additives for flame retardancy can be used alone, or two or more can be used in combination.

The heat resistance and flame retardancy of the resin can be further improved by adding a trace amount of Lewis acid to the flame retardant resin composition containing the flame retardant C of the present invention. As the Lewis acid, conventionally known ones can be widely used, and examples thereof include zinc chloride and iron chloride. These Lewis acids can be used alone or in combination of two or more. Further, these Lewis acids are preferably blended usually in an amount of about 0.01 to 0.6 parts by weight with respect to the total amount of the flame-retardant resin composition.

The flame-retardant resin composition of the present invention may be blended with various conventionally known resin additives as long as the excellent properties are not impaired. Examples of the resin additive include a flame retardant other than the above, an anti-drip agent (anti-drip agent), an ultraviolet absorber, a light stabilizer, an antioxidant, a light-blocking agent, a metal deactivator, a quencher, a heat stabilizer, Lubricants, release agents, coloring agents, antistatic agents, anti-aging agents, plasticizers, impact strength improvers, compatibilizers and the like can be mentioned.

The ultraviolet absorber absorbs light energy and undergoes intramolecular proton transfer to form a keto-type molecule (benzophenone or benzotriazole),
Alternatively, it is a component for releasing and detoxifying as thermal energy by cis-trans isomerization (cyanoacrylate). As a specific example, for example, 2,4-
2-hydroxybenzophenones such as dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); '-Hydroxy-5'
-Methylphenyl) benzotriazole, 2- (2'-
Hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-
t-butylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3 ', 5'-di-t-butylphenyl)
-5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ',
5′-dicumylphenyl) benzotriazole, 2,
2- (2'-hydroxyphenyl) benzotriazoles such as 2'-methylenebis (4-t-octyl-6-benzotriazolyl) phenol, phenyl salicylate, resorcinol monobenzoate, 2,4-di-t
-Butylphenyl-3 ', 5'-di-t-butyl-4'
Benzoates such as -hydroxybenzoate, hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2-ethyl-2'-ethoxyoxanilide,
Substituted oxanilides such as 2-ethoxy-4'-dodecyl oxanilide, and ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate And the like.

The light stabilizer is a component for decomposing the hydroperoxide generated by light energy to produce stable NO—radicals, N—OR, and N—OH and stabilizing it. Light stabilizers may be mentioned. As specific examples, for example, 2, 2,
6,6, -tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-
Piperidyl benzoate, bis (2,2,6,6-tetramethyl-4-piperidyl sebacate, bis (1,2,2
2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-
Piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,
2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3 ′, 5′-di-tert-butyl-4 -Hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4
-Piperidinol / diethyl succinate polycondensate, 1,6
-Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / dibromoethane polycondensate, 1,6
-Bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-t-octylamino-s-triazine polycondensate, 1,6-bis (2,2 6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s
-Triazine polycondensates and the like.

The antioxidant is a component for stabilizing generated peroxide radicals such as hydroperoxy radicals or decomposing generated peroxides such as hydroperoxides during thermoforming or light exposure. is there. Examples of the antioxidant include a hindered phenol-based antioxidant and a peroxide decomposer. The former acts as a radical chain inhibitor, and the latter acts to decompose peroxides generated in the system into more stable alcohols to prevent autoxidation.

Examples of the hindered phenol-based antioxidants include 2,6-di-t-butyl-4-methylphenol, styrenated phenol, n-octadecyl 3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-t-butyl-6
-(3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1-
(2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 4,4′-butylidenebis (3-methyl-6
-T-butylphenol), 4,4'-thiobis (3-
Methyl-6-t-butylphenol), alkylated bisphenol, tetrakis [methylene 3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1- Dimethylethyl] -2,4,8,
Examples thereof include 10-tetraoxaspiro [5.5] undecane.

Examples of the peroxide decomposer include organic phosphorus peroxide decomposers such as tris (nonylphenyl) phosphite, triphenyl phosphite, and tris (2,4-di-t-butylphenyl) phosphite. , Dilauryl-3,3'-thiodipropionate, dimyristyl-
3,3′-thiodipropionate, distearyl-3,
An organic sulfur-based peroxide decomposer such as 3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole, etc. Can be illustrated.

The light-shielding agent is a component for preventing light from reaching the bulk of the polymer. Specific examples include rutile-type titanium oxide (TiO ₂ ) and zinc oxide (Zn).
O), chromium oxide (Cr ₂ O ₃ ), cerium oxide (CeO)
₂ ) and the like.

The metal deactivator is a component for deactivating heavy metal ions in the resin by a chelate compound.
Specific examples thereof include benzotriazole and its derivatives (specifically, 1-hydroxybenzotriazole and the like).

The quencher is a component for deactivating functional groups such as photo-excited hydroperoxide and carbonyl group in the polymer by energy transfer, and specific examples thereof include organic nickel.

For the purpose of imparting antifogging property, antifungal property, antibacterial property or other functions, various conventionally known additives may be further added.

Production of Flame-Retardant Resin Composition of the Present Invention The flame-retardant resin composition of the present invention is obtained by adding the above-mentioned flame retardant, if necessary, an inorganic filler and a halogen-free organic phosphorus compound to a thermoplastic resin or a thermosetting resin. A predetermined amount or an appropriate amount of a fluororesin, various additives for flame retardancy, and other additives are weighed and added, followed by mixing and kneading by a known method. For example, an extruder such as a single-screw extruder or a twin-screw extruder, a Banbury mixer, a pressure kneader,
The resin composition of the present invention can be obtained by kneading using a kneader such as a two-roll mill. When it is necessary to mix a liquid, the mixture can be kneaded with the above-described extruder or kneader using a known liquid injection device.

The flame-retardant resin molded article of the present invention By molding the flame-retardant resin composition of the present invention, a flame-retardant resin molded article can be obtained. For example, press molding, injection molding, from conventionally known molding means such as extrusion molding,
It is a matter of course that resin sheets, sheets, films, extruded articles of various shapes such as irregularly shaped articles can be manufactured, and it is also possible to manufacture resin sheets having a two-layer or three-layer structure using a co-extrusion kneader or the like. It is possible.

The flame-retardant resin composition and the flame-retardant resin molded product of the present invention thus obtained can be used for electric / electronic / communication,
It can be used in a wide range of industrial fields such as agriculture, forestry and fisheries, mining, construction, food, textile, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood, furniture, printing, musical instruments, etc.

More specifically, the flame-retardant resin composition and the flame-retardant resin molded article of the present invention can be used for a printer, a personal computer, a word processor, a keyboard, a PDA (small information terminal), a telephone, a facsimile, a copier, ECR (electronic cash register), calculator, electronic organizer, electronic dictionary, card, holder,
Office / OA equipment such as stationery, washing machine, refrigerator, vacuum cleaner,
Home appliances such as microwave ovens, lighting equipment, game consoles, irons and kotatsu, TVs, VTRs, video cameras, radio and cassette players, tape recorders, mini discs, CD players, speakers, liquid crystal displays and other AV equipment, connectors,
It is used for electrical and electronic parts such as relays, capacitors, switches, printed boards, coil bobbins, semiconductor sealing materials, electric wires, cables, transformers, deflection yokes, distribution boards, watches, etc., and for communication equipment.

Further, the flame-retardant resin composition and the flame-retardant resin molded article of the present invention can be used for seats (filling, dressing, etc.), belts, ceiling covering, compatible tops, armrests, door trims, rear package trays, carpets, mats. , Sun visors, foil covers, mattress covers, airbags, insulating materials, suspenders, suspenders, electric wire covering materials, electrical insulation materials, paints, coating materials, overlays, flooring, corner walls, deck panels, covers Automobiles, vehicles, ships, aircraft, and building materials such as plywood, plywood, ceiling boards, partition boards, side walls, carpets, wallpaper, wall coverings, exterior coverings, interior coverings, roof coverings, soundproofing boards, heat insulating boards, window coverings, etc. , Clothing, curtains, sheets, plywood, synthetic fiber, carpets, entrance mats, sheets, buckets, hoses, containers, glasses, bags, cases, goggles, skis, rackets, tents, musical instruments It is used to the lifestyle and sports equipment for various applications.

[0132]

EXAMPLES The present invention will be specifically described below with reference to Synthesis Examples, Examples and Comparative Examples. In the following, “parts” and “%” mean “parts by weight” and “% by weight” unless otherwise specified.

Synthesis Example 1 (Compound A; synthesis of a phenoxyphosphazene compound having a crosslinked structure with paraphenylene) 2.04 mol (196 g) of the same mole as phenol (82 g)
g) is azeotropically dehydrated with toluene from sodium hydroxide to give about 1200% of a 20% sodium phenolate solution in toluene.
g was prepared.

In parallel with the above reaction, dichlorophosphazene oligomer (58.57% trimer, 12.26 tetramer)
%, Pentamer and hexamer 11.11%, heptamer 2.82
580 g of a 20% chlorobenzene solution containing 115.9 g in a 2-liter four-necked flask, and stirred under stirring to prepare a separately prepared hydroquinone dilithium salt 0.15 g. A mole (18.3 g) of a 10% toluene solution was added dropwise. After the dropwise addition, the mixture was stirred and reacted at 50 ° C. for 5 hours. Subsequently, about 1200 g of a 20% toluene solution of sodium phenolate prepared above was added dropwise with stirring, and the mixture was stirred and reacted at 100 ° C. for 8 hours.

After the completion of the reaction, the reaction mixture was concentrated, poured into 3 liters of a mixed solvent of water / methanol = 1/1 by volume under stirring, neutralized with dilute sulfuric acid, and filtered. Then
The mixture was washed twice with 3 liters of a mixed solvent of water / methanol = 1/1 by volume, filtered, and dried under vacuum at 80 ° C. and 20 mmHg for 11 hours to obtain 220 g of a slightly yellow powder.

The crosslinked phenoxyphosphazene compound obtained above did not show a clear melting point, and the decomposition starting temperature by TG / DTA analysis was 305 ° C. Further, from the phosphorus content and the CHN elemental analysis value, the composition of this crosslinked phenoxyphosphazene compound was almost [N = P (-Op-
Ph-O-) _0.15 (-O-Ph) _1.7 ].

Synthesis Example 2 (Compound B: 2,2-bis (p-
Synthesis of a phenoxyphosphazene compound having a crosslinked structure with an (oxyphenyl) propane group) 86.7 g (0.38 mol) of bisphenol-A and 460 ml of tetrahydrofuran (THF) were placed in a two-liter four-necked flask, and the internal mixture was stirred. Liquid temperature 19 ℃
And 3.5 g (0.5 mol) of metal Li was cut and charged. After completion of the charging, the temperature was raised to 61 ° C. over 1 hour, and stirring was continued at 61 ° C. to 68 ° C. for 4 hours. After completion of the reaction, the lithium salt of bisphenol-A in the reaction mixture became a white slurry.

215.6 g (2.25 mol) of phenol
Then, 500 ml of toluene and 500 ml of toluene were put into a three-liter four-necked flask, and 34.5 g (1.5 mol) of metallic Na was cut and charged while maintaining the internal liquid temperature at 25 ° C. with stirring. The temperature is raised to 77 ° C over 4 hours after completion of the charging, 77 ° C to 113 ° C
Stirring was continued at C for 3 hours. After completion of the reaction, sodium phenolate of the reaction mixture became a white slurry.

Dichlorophosphazene oligomer (concentration 3
7.01%, monochlorobenzene solution, trimer 58.5
7%, tetramer 12.26%, pentamer and hexamer 11.11
313.13 g (1.0 mol) in a 5 liter four-necked flask, and while stirring, the internal liquid temperature was lowered. While maintaining the temperature at 20 ° C., the lithium salt solution of bisphenol-A was added dropwise over 1 hour. The contents became pale yellow milky. Then, while stirring, the sodium phenolate solution was added dropwise over 1 hour while maintaining the internal liquid temperature at 20 ° C. The contents became a brown slurry. 13 hours at 47 ° C after completion of dropping,
Stirring was continued. It became a light brown slurry.

After the completion of the reaction, the reaction mixture was concentrated. Then, the mixture was washed three times with 3 liters of 2% NaOH, filtered, washed three times with 3 liters of a mixed solvent of water / methanol = 1/1 by volume, filtered, and dried under vacuum at 80 ° C. and 20 mmHg for 11 hours. A powder was obtained. Yield 208.
67 g, 86.50 yield based on dichlorophosphazene
%.

The hydrolyzed chlorine in the obtained compound was 0.93.
%, Decomposition temperature is 296.0 ° C, and 5% weight loss temperature is 307.
7 ° C. The composition of the phosphorus content and CHN final product elemental analysis values, [N = P (-O- Ph-C (CH 3) 2
-Ph-O-) _0.25 (-O-Ph) _1.50 ].

Synthesis Example 3 (Compound C: Synthesis of Phenoxyphosphazene Compound Having Cross-Linked Structure with Metaphenylene) Using resorcinol instead of hydroquinone, the reaction and treatment were carried out in the same manner as in Synthesis Example 1, and [N = P (-O -M-P
h-O-) _0.15 (-O-Ph) _1.7 ]. This crosslinked phenoxyphosphazene compound did not show a clear melting point, and the decomposition start temperature by TG / DTA analysis was 300 ° C.

Example 1 75 parts of an aromatic polycarbonate resin and 25 parts of an ABS resin
Of the compound A 15 produced in Synthesis Example 1
Parts and 0.2 parts of PTFE are added and mixed with a mixer.
The mixture was melt-kneaded using a Labo Plastomill to obtain a flame-retardant resin composition.

A test piece having a thickness of 1/8 inch was prepared from this composition by a heat press, and evaluated for flame retardancy based on the UL-94 test method and the heat distortion temperature according to ASTM D-648. A measurement was made. As a result, the flame retardancy was V-0 and the heat distortion temperature was 108 ° C., and no juicing was observed during molding.

Example 2 A sample was prepared and evaluated in the same manner as in Example 1 except that the compound B prepared in Synthesis Example 2 was used instead of the compound A. As a result, the flame retardancy was V-0 and the heat distortion temperature was 111 ° C., and no juicing was observed during molding.

Example 3 A sample was prepared and evaluated in the same manner as in Example 1 except that Compound C prepared in Synthesis Example 3 was used instead of Compound A. As a result, the flame retardancy was V-0 and the heat distortion temperature was 106 ° C., and no juicing was observed during molding.

Example 4 A sample was prepared in the composition of Example 1 without adding PTFE, and the flame retardancy and the heat distortion temperature were evaluated. As a result, the flame retardancy was V-0 and the heat distortion temperature was 109 ° C., and no juicing was observed during molding.

COMPARATIVE EXAMPLE 1 Instead of compound A, tricilyl phosphate was used.
Sample preparation and evaluation were performed in the same manner as in Example 1. As a result,
The flame retardancy was V-2 and the heat distortion temperature was 82 ° C, and juicing was observed during molding.

Reference Example 1 A stirring rod, a condenser, a dropping funnel and a flask equipped with a thermometer were charged with 460 g (3 mol) of phosphorus oxychloride, 110 g (2 mol) of resorcinol, and 94.1 g (1 mol) of phenol.
And 9 g of aluminum chloride (catalyst) at the same time
0 ° C. and then 564.6 g of phenol (6
Mol) was added and reacted. After washing the reaction mixture with water, triphenyl phosphate was distilled off under a high temperature vacuum, and condensed phosphoric acid diphenyl ester 515 cross-linked with resorcinol was added.
g was obtained.

Quality of the condensed phosphoric acid diphenyl ester: yellow liquid, average molecular weight = 540,% P = 10.6,
Acid value 2.2.

Comparative Example 2 A sample was prepared and evaluated in the same manner as in Example 1 except that Compound A was replaced with diphenyl phosphate condensed with resorcinol (obtained in Reference Example 1). As a result, the flame retardancy was V-2 and the heat distortion temperature was 89 ° C., and juicing was observed during molding.

Comparative Example 3 A sample was prepared and evaluated in the same manner as in Example 1 without adding a flame retardant. As a result, the test piece burned, and showed no flame retardancy. The heat distortion temperature was 111 ° C.

Example 5 Compound A (15 parts) was added to a resin composed of 70 parts of poly (2,6-dimethyl-1,4-phenylene) oxide and 30 parts of rubber-modified impact-resistant polystyrene, and mixed with a mixer. Using a Labo Plastmill to obtain a flame-retardant resin composition.

A test piece having a thickness of 1/8 inch was prepared from this composition by a heat press, and evaluated for flame retardancy based on the UL-94 test method and the heat distortion temperature according to ASTM D-648. A measurement was made. As a result, the flame retardancy was V-0 and the heat distortion temperature was 130 ° C., and no juicing was observed during molding.

Example 6 A sample was prepared and evaluated in the same manner as in Example 5, except that Compound B was used instead of Compound A. As a result, the flame retardancy is V-0,
The heat distortion temperature was 131 ° C., and no juicing was observed during molding.

Example 7 A sample was prepared and evaluated in the same manner as in Example 5, except that Compound C was used instead of Compound A. As a result, the flame retardancy is V-0,
The heat distortion temperature was 128 ° C., and no juicing was observed during molding.

Comparative Example 4 Using triphenyl phosphate instead of compound A,
Sample preparation and evaluation were performed in the same manner as in Example 5. As a result,
The flame retardancy was V-2 and the heat distortion temperature was 110 ° C, and juicing was observed during molding.

Comparative Example 5 A sample was prepared and evaluated in the same manner as in Example 5, except that Compound A was replaced with diphenyl phosphate condensed with resorcinol (obtained in Reference Example 1). As a result, the flame retardancy was V-2, the heat distortion temperature was 115 ° C.,
Juicing was observed during molding.

Comparative Example 6 When a sample was prepared and evaluated in the same manner as in Example 5 without adding a flame retardant, the test piece burned and showed no flame retardancy. The heat distortion temperature was 133 ° C.

Example 8 A varnish was prepared by adding 10 parts of Compound A to 100 parts of a bisphenol-A type epoxy resin, impregnating the varnish with a glass cloth, and then drying to prepare a prepreg.
Subsequently, a predetermined number of prepregs were stacked and heated and pressed at 160 ° C. or higher to produce a glass epoxy plate having a thickness of 1/16 inch, which was cut into a specified size to obtain a test piece. Using this test piece, flame retardancy was evaluated based on the UL-94 test method, and as a result, flame retardancy V-0 was obtained. No juicing was observed during hot pressing.

Example 9 A sample was prepared and evaluated in the same manner as in Example 8, except that Compound C was used instead of Compound A. As a result, the flame retardancy was V-0, and no juicing was observed during hot pressing.

Comparative Example 7 In place of Compound A, a sample was prepared and evaluated in the same manner as in Example 8, except that a condensed phosphoric acid diphenyl ester crosslinked with resorcinol (obtained in Reference Example 1) was used. As a result, the flame retardancy was V-2, and juicing was observed during hot pressing.

Comparative Example 8 A sample was prepared and evaluated in the same manner as in Example 8 without adding a flame retardant. As a result, the test piece burned and showed no flame retardancy.

Examples 10 to 13 General formula-[-N = P (-O-crosslinking group -O-) x (-O-Ph) synthesized in the same manner as in Synthesis Example 2.
Using the compound represented by y-] n-, a flame retardancy test was performed in the same manner as in Example 1. Table 1 shows the results.

[0165]

[Table 1]

In Table 1, Tm (° C.) is the melting temperature by thermogravimetric analysis (TG / DTA analysis), T5 (° C.) is the temperature of 5% weight loss by thermogravimetric analysis, and Td (° C.) is the thermogravimetric analysis. Is the decomposition temperature.

As is evident from Table 1, the resin compositions containing the flame retardant comprising the compound represented by the above general formula all had good moldability, and no juicing was observed.

Synthesis Example 4 (Compound D: Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4′-Sulfonyldiphenylene (Bisphenol-S Residue)) In a 1-liter four-necked flask, 1.28 mol of phenol ( 121.14 g) and bisphenol-S 0.01
7 mol (4.26 g) and tetrahydrofuran (TH
F) Dissolve in 500 ml, add 7.6 g of crushed metal sodium at 25 ° C. or less,
The mixture was stirred at 61 ° C. to 68 ° C. for 6 hours to prepare a sodium phenolate mixed solution.

In parallel with the above reaction, dichlorophosphazene oligomer (58.57% trimer, 12.26 tetramer)
%, 5 and hexamers 11.11%, heptamers 2.82%, 8
290 g of a 20% chlorobenzene solution containing 0.5 unit mol (58 g) is prepared in a two-liter four-necked flask, and 25
The above-mentioned sodium phenolate mixed solution prepared above was added dropwise under cooling and stirring at a temperature of not more than ° C. After dripping, 71-73
The mixture was stirred and reacted at 15 ° C for 15 hours.

After the completion of the reaction, the reaction mixture was concentrated and redissolved in 500 ml of chlorobenzene.
H water washing three times, 5% sulfuric acid washing, 5% sodium bicarbonate water washing, and water washing three times, concentration to dryness, and a pale yellow waxy substance 108
g was obtained. Yield 93.5%.

The weight average molecular weight (Mw) of this product by GPC analysis was 810 in terms of polystyrene.
Melting temperature (Tm) by DTA analysis is 103 ° C and 5%
Weight loss temperature (T5) and decomposition onset temperature (Td) are each 3
30 and 347 ° C.

The residual chlorine content was 0.09%, and from the phosphorus content and CHN elemental analysis, the composition of this product was almost [N = P (-O-Ph-SO ₂ -Ph-O-)].
_0.025 (-O-Ph) _1.95 ].

Synthesis Examples 5 to 6 (Compound E and Compound F:
4,4'-sulfonyldiphenylene (bisphenol-
Synthesis of Phenoxyphosphazene Having Cross-Linked Structure by S Residue) 1.254 mol (118.03 g) of phenol and 0.033 mol (8.26 g) of bisphenol-S [or 1.122 mol (105.60 g) of phenol 0.099 mol (24.77 g) of bisphenol-S], and the reaction and post-treatment were carried out in the same manner as in Synthesis Example 4 to obtain a pale yellow waxy substance. As a result of analysis, the following compounds were confirmed. . Compound E: [N = P (-O -Ph-SO 2 -Ph-O-) 0.05 (-
O-Ph) _1.90 ] Yield 91.5%, residual chlorine = 0.01% or less, Mw = 8
20, Tm = 103 ° C., T5 = 332 ° C., Td = 347
℃ Compound F: [N = P (-O -Ph-SO 2 -Ph-O-) 0.15 (-
O-Ph) _1.70 ] yield 90.0%, residual chlorine = 0.11%, Mw = 85
0, Tm = 102 ° C., T5 = 333 ° C., Td = 355
° C.

Synthesis Examples 7 and 8 (Compound G and Compound H:
Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4'-Oxydiphenylene Group) Bis (4-hydroxyphenyl) ether 13.4 g
(0.066 mol) and 111.7 g of phenol (1.1
88 mol) [or bis (4-hydroxyphenyl) ether 26.8 g (0.132 mol) and phenol 9
9.3 g (1.056 mol)] and metallic Na 27.6
Using g (1.2 mol), the same reaction and treatment were carried out on the same scale as in Synthesis Example 4 to obtain the following highly viscous compound. Compound G: [N = P (-O-Ph-O-Ph-O-) _0.1 (-O-
Ph) _1.8 ] yield 99.8%, residual chlorine = 0.01% or less, Mw = 1
510, Tm = not detectable, T5 = 346 ° C., Td = 3
53 ° C Compound H: [N = P (-O-Ph-O-Ph-O-) _0.2 (-O-
Ph) _1.6 ] yield 97.9%, residual chlorine = 0.11%, Mw = 195
0, Tm = not detectable, T5 = 318 ° C., Td = 37
5 ° C.

Synthesis Examples 9 to 10 (Compound I and Compound J:
Synthesis of Phenoxyphosphazene Having Cross-Linked Structure with 4,4′-thiodiphenylene Group) Using 14.4 g (0.066 mol) of 4,4′-thiodiphenol [or 28.8 g (0.132 mol)] ,
Reaction and treatment were carried out in the same manner as in Synthesis Examples 7 and 8, to obtain the following highly viscous compounds. Compound I: [N = P (-O-Ph-S-Ph-O-) _0.1 (-O-
Ph) _1.8 ] yield 98.8%, residual chlorine = 0.09%, Mw = 169
0, Tm = not detectable, T5 = 340 ° C., Td = 34
4 ° C Compound J: [N = P (-O-Ph-S-Ph-O-) _0.2 (-O-
Ph) _1.6 ] yield 95.1%, residual chlorine = 0.01%, Mw = 305
0, Tm = not detectable, T5 = 344 ° C., Td = 348
° C.

Synthesis Examples 11 to 12 (Compound K and Compound L: Synthesis of Phenoxyphosphazene Having Cross-Linked Structure by 4,4′-Diphenylene Group) 12.3 g (0.066 mol) of 4,4′-diphenol
Using [or 24.6 g (0.132 mol)], the reaction and treatment were carried out in the same manner as in Synthesis Examples 7 and 8, to obtain the following highly viscous compounds. Compound K: [N = P (-O-Ph-Ph-O-) _0.1 (-OP
h) _1.8 ] yield 99.9%, residual chlorine = 0.01%, Mw = 159
0, Tm = not detectable, T5 = 348 ° C., Td = 349
° C Compound L: [N = P (-O-Ph-Ph-O-) _0.2 (-OP
h) _1.6 ] yield 97.0%, residual chlorine = 0.11%, Mw = 190
0, Tm = not detectable, T5 = 345 ° C., Td = 347
° C.

Example 14 75 parts of aromatic polycarbonate resin and 25 parts of ABS resin
Of phenoxyphosphazene (compound D) having a crosslinked structure with 4,4'-sulfonyldiphenylene (bisphenol-S residue) and PTFE
After adding 0.5 part and mixing with a mixer, the mixture was melt-kneaded using a Labo Plastomill to obtain a flame-retardant resin composition.

A test piece having a thickness of 1/8 inch was prepared from this composition by a hot press, and evaluated for flame retardancy based on the UL-94 test method and the heat distortion temperature according to ASTM D-648. A measurement was made. As a result, there was no dripping of the test piece, the flame retardancy was V-0 and the heat deformation temperature was 111 ° C., and no juicing was observed during molding.

Example 15 Using 18 parts of compound E, a sample was prepared and evaluated in the same manner as in Example 14 without adding PTFE. As a result, there was no melting dripping that ignites the cotton of the test piece, the flame retardancy was V-0, the heat deformation temperature was 112 ° C., and no juicing was observed during molding. From this result, it was confirmed that the compound was a compound capable of exhibiting desired flame retardancy without using PTFE, and proved to be a true non-halogen flame retardant.

Examples 16 to 22 Samples were prepared and evaluated in the same manner as in Example 13 using Compounds FL. Table 2 shows the results.

[0181]

[Table 2]

Example 23 To a resin consisting of 70 parts of poly (2,6-dimethyl-1,4-phenylene) oxide and 30 parts of rubber-modified impact-resistant polystyrene, 15 parts of phenoxyphosphazene having a crosslinked structure of compound E was added. After mixing with a mixer, the mixture was melt-kneaded using a Labo Plastomill to obtain a flame-retardant resin composition.

A test piece having a thickness of 1/8 inch was prepared from this composition by a hot press, and evaluated for flame retardancy based on the UL-94 V test method and the heat distortion temperature according to ASTM D-648. Was measured. As a result, the flame retardancy was V-0 and the heat deformation temperature was 131 ° C., and no juicing was observed during molding.

Example 24 A sample was prepared and evaluated in the same manner as in Example 23, except that Compound H was used instead of Compound E. As a result, the flame retardancy is V-
0, the heat distortion temperature was 133 ° C., and no juicing was observed during molding.

Example 25 A sample was prepared and evaluated in the same manner as in Example 23, except that Compound J was used instead of Compound E. As a result, the flame retardancy is V-
0, the heat deformation temperature was 130 ° C., and no juicing was observed during molding.

Example 26 A varnish was prepared by adding 10 parts of Compound D to 100 parts of a bisphenol-A type epoxy resin, impregnating the varnish with a glass cloth, and then drying to prepare a prepreg.
Next, a predetermined number of prepregs were stacked and heated and pressed at 160 ° C. or higher to produce a glass epoxy plate having a thickness of 1/16 inch, and cut into prescribed dimensions to obtain test pieces. Using this test piece, flame retardancy was evaluated based on the UL-94 test method, and as a result, flame retardancy V-0 was obtained. No juicing was observed during hot pressing.

Example 27 A sample was prepared and evaluated in the same manner as in Example 26, except that Compound H was used instead of Compound E. As a result, the flame retardancy was V-0.
No juicing was observed during hot pressing.

Example 28 A sample was prepared and evaluated in the same manner as in Example 26, except that Compound J was used instead of Compound E. As a result, the flame retardancy was V-0.
No juicing was observed during hot pressing.

Synthesis Example 13 (Synthesis of chlorphosphazene) 2512 g (12 mol) of 99.5% phosphorus pentachloride (PCl ₅ ), and 99.5% ammonium chloride (NH ₄ Cl) 68
8g (12.8 mol), 97.0% zinc chloride (ZnCl
₂ ) 20 g (0.16 mol) and 5 liters of monochlorobenzene (MCB) were put into a reaction vessel equipped with a temperature control device, a stirrer and a reflux device, and the reaction was initially started at 24 ° C., and the temperature was gradually raised. The temperature was raised to 130 ° C. three hours after the start of the reaction. After further refluxing with stirring at 130 ° C. to 134 ° C. for 2 hours, the reaction mixture was filtered, and 76 g of a white filtration residue was obtained.
And chlorphosphazene as a nearly colorless and transparent MCB solution (6883 g, 1343 g in terms of 100% chlorophosphazene, chlorphosphazene concentration in the solution of 1).
9.51%). 96.56% yield (vs. phosphorus pentachloride).

As a result of analysis by ³¹ P-NMR, the trimer m
= 3 (where m represents m in the above general formula): 5
4%, tetramer m = 4: 19%, pentamer m ≧ 5: 27%.

This solution was concentrated to give a 39.5% chlorophosphazene solution, which was used as a raw material for Synthesis Example 14.

Synthesis Example 14 (Synthesis of phenoxyphosphazene) 2931 g (31.14 mol) of phenol (PhOH), 596.67 g (25.95 mol) of metallic Na and 7 liters of tetrahydrofuran (THF) were added to a temperature controller and a stirrer. And the mixture was refluxed for 8 hours with stirring. The reaction mixture is slightly colored. next,
A solution obtained by dissolving the 39.5% chlorophosphazene solution (3172.41 g) obtained in Synthesis Example 13 in 5.5 L of THF was added dropwise to this solution at a temperature of 42 ° C to 79 ° C. After completion of the dropwise addition, reflux was continued at 78 ° C. for 10 hours with stirring.

Next, the reaction mixture was concentrated and dissolved in 8 liters of monochlorobenzene, 5 liters of water and 3 liters of a 5% aqueous NaOH solution. This was washed in the following order. 5% NaOH aqueous solution twice with 7 liters, 5% hydrochloric acid 7
Once with liter, once with 7 liter of 7% NaHCO3 aqueous solution and twice with 7 liter of water. After washing, MgSO ₄ was added, dried and concentrated. Finally, vacuum drying was performed at 80 ° C. and 3 torr or less for 12 hours to obtain 2437 g of yellow sherbet-like phenoxyphosphazene. Yield 97.5%.

The analysis results are as follows. ³¹ P-NMR
Thus, trimer m = 3: 55%, tetramer m = 4: 18%,
Pentamer m ≧ 5: 27%, weight average molecular weight Mw from GPC
= 720, mp = 109 ° C, 5% weight loss temperature Td (5%)
= 343 ° C, decomposition temperature Td = 366 ° C,% residue after thermal decomposition (600 ° C) = 19%, residual PhOH = 0.038 w
t%, residual MCB = 0.042 wt%, residual chlorine = 0.
102%.

Example 29 75 parts of an aromatic polycarbonate resin and 25 parts of an ABS resin
Part of the resin, 15 parts of phenoxyphosphazene obtained in Synthesis Example 14 as a flame retardant and potassium titanate fiber (manufactured by Otsuka Chemical Co., Ltd., trade name: TISMO N-10)
2, the same shall apply hereinafter) 7.5 parts, and after mixing with a mixer,
The mixture was melt-kneaded using a Labo Plastomill to obtain a flame-retardant resin composition.

From this composition, 1/16
An inch-thick test was prepared, and the flame retardancy was evaluated based on the UL-94 test method, and the heat distortion temperature was measured according to ASTM D-648. Further, at the time of the flame retardancy test, the presence or absence of flaming particles (drip) that ignite cotton, the presence or absence of generation of volatile gas during kneading of Labo Plastomill, and the change in appearance after molding of the test piece were examined. Table 3 shows the results.

Examples 30 to 31 In Example 29, except that kaolin (a reagent of Wako Pure Chemical Industries, Ltd.) or mica (trade name: Clarite Mica 400W, manufactured by Kuraray Co., Ltd.) was used instead of the potassium titanate fiber. In the same manner as in Example 29, a flame-retardant resin composition was obtained. The flame retardancy of these compositions was evaluated in the same manner as in Example 29. Table 3 shows the results.

Examples 32 to 35 Flame-retardant resin compositions were obtained in the same manner as in Example 29 except that Compounds E to H were used instead of Phenoxyphosphazene of Synthesis Example 2. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

Example 36 In Example 29, poly (2,6-dimethyl-butene) was used in place of the resin composed of the polycarbonate resin and the ABS resin.
A flame-retardant resin composition was obtained in the same manner as in Example 29 except that a resin composed of 60 parts of (1,4-phenylene) oxide and 40 parts of rubber-modified impact-resistant polystyrene was used. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

Example 37: Based on 100 parts of a bisphenol-A type epoxy resin,
A varnish was prepared by adding 15 parts of the phenoxyphosphazene synthesized in Synthesis Example 14 and 7.5 parts of potassium titanate fiber, and the varnish was impregnated with a glass cloth and dried to prepare a prepreg. Subsequently, a predetermined number of the prepregs were stacked and heated and pressed at 160 ° C. or higher to produce a glass epoxy plate having a thickness of 1/16 inch, which was cut into a specified size to obtain a test piece. Using this test piece, a combustion test based on the UL-94 test method and a measurement of the heat distortion temperature were performed according to the above-described methods. Table 3 shows the results.

Comparative Example 9 Example 29 was repeated except that potassium titanate fiber was not blended.
In the same manner as in the above, a resin composition was obtained. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

Comparative Example 10 Example 36 was repeated except that potassium titanate fiber was not blended.
In the same manner as in the above, a resin composition was obtained. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

Comparative Example 11 Example 37 was repeated except that potassium titanate fiber was not blended.
In the same manner as in the above, a resin composition was obtained. The flame retardancy of this composition was evaluated in the same manner as in Example 29. Table 3 shows the results.

[0204]

[Table 3]

Synthesis Example 15 (Synthesis of phenoxyphosphazene having 4-cyanophenoxy group) 0.44 mol of 4-cyanophenol was placed in a two-liter four-necked flask equipped with a stirrer, a heating device, a thermometer and a dehydrator. (52.4 g), phenol 2.20 mol (207.0 g), sodium hydroxide 2.64 mol (1
05.6 g) and 1000 ml of toluene were added. The mixture was heated to reflux to remove water from the system, and a toluene solution of cyanophenol and sodium salt of phenol was prepared.

To a toluene solution of this cyanophenol and the sodium salt of phenol was added 1 unit mol (11
5.9 g) of dichlorophosphazene oligomer (trimer 59%, tetramer 12%, 5 and hexamer 11%, heptamer 3
%, 580 g of a 20% chlorobenzene solution containing an octamer or more cyclic and linear compound (15%) was added dropwise at an internal temperature of 30 ° C. or lower while stirring. This mixed solution is
After refluxing for 5 hours, a 5% aqueous sodium hydroxide solution was added to the reaction mixture, and the mixture was washed twice. Next, the organic layer was neutralized with dilute sulfuric acid, washed twice with water, filtered, concentrated and dried under vacuum (vacuum drying conditions: 80 ° C., 5 mmHg, 12 hours) to obtain 220 g of a slightly yellow viscous liquid. Got. The yield calculated from the dichlorophosphazene oligomer used was 92%.

The remaining hydrolyzable chlorine in the product was 0.09%
And the ¹ H-NMR spectrum is 7.6 to 6.6 ppm,
³¹ P-NMR spectrum is 10-6, -11-14,
It showed a peak in the range of -16 to -21 ppm, and the weight average molecular weight measured by GPC was 1500 (a value in terms of polystyrene).

From the results of elemental analysis of carbon, hydrogen, nitrogen and phosphorus, the composition of this product was [N = P (OC ₆ H ₄ CN)
_0.33 (OPH) _1.67 ], and this composition was in agreement with the charging ratio of 4-cyanophenol to phenol, and it was confirmed that the target compound was synthesized. This product did not show a definite melting point and its decomposition temperature by TG / DTA analysis was 327 ° C.
showed that.

Synthesis Examples 16 to 19 The phenoxyphosphazene compound having a 4-cyanophenoxy group was synthesized in the same manner as in Synthesis Example 15 except that the proportions of 4-cyanophenol and phenol used in Synthesis Example 15 were changed. Table 4 shows the results.

Elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus, and ¹ H-NMR and ³¹ P-NMR of these products
From the spectrum measurement results, it was confirmed that the composition of the product matched the charge ratio of 4-cyanophenol and phenol, and that the desired products were synthesized.

[0211]

[Table 4]

Synthesis Example 20 An isopropylphenoxyphosphazene compound having a 4-cyanophenoxy group was synthesized in the same manner as in Synthesis Example 15 except that the phenol used in Synthesis Example 15 was changed to 4-isopropylphenol. Table 5 shows the results. From the results of elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus of the product and the measurement results of ¹ H-NMR and ³¹ P-NMR spectrum, the composition of the product was 4-cyanophenol and 4
It was confirmed that the target product could be synthesized in accordance with the charging ratio of -isopropylphenol.

Synthesis Example 21 A naphthoxyphosphazene compound having a 4-cyanophenoxy group was synthesized in the same manner as in Synthesis Example 15 except that phenol used in Synthesis Example 15 was changed to 2-naphthol. Table 5 shows the results. Elemental analysis and ¹ H-NMR of carbon, hydrogen, nitrogen, chlorine and phosphorus of this product and
^From the measurement results of the ³¹ P-NMR spectrum, it was confirmed that the composition of the product was in agreement with the charging ratio of 4-cyanophenol and 2-naphthol, and the target compound was synthesized.

Synthetic Example 22 The same procedure as in Synthetic Example 15 was carried out except that phenol used in Synthetic Example 15 was changed to N-propanol and 4-cyanophenol was changed to 2-cyanophenol, and their sodium salts were prepared with metallic sodium. Was used to synthesize a propoxyphosphazene compound having a 4-cyanophenoxy group. Table 5 shows the results. The composition of these products carbon, hydrogen, elemental analysis of nitrogen and phosphorus, ¹ H-NMR
And ³¹ P-NMR spectrum, it was confirmed that the target compound was synthesized according to the charged ratio of 2-cyanophenol and N-propanol.

Synthesis Example 23 The procedure of Synthesis Example 15 was repeated except that the phenol used in Synthesis Example 15 was replaced with 2-ethylhexanol, and the sodium salt of 2-ethylhexanol and 4-cyanophenol was prepared with metallic sodium. -An ethylhexyloxyphosphazene compound having a cyanophenoxy group was synthesized. Table 5 shows the results. Elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus of this product and ¹ H-NM
From the measurement results of the R and ³¹ P-NMR spectra, it was confirmed that the composition of the product coincided with the charging ratio of 4-cyanophenol and 2-ethylhexanol, and that the desired product was synthesized.

Synthesis Example 24 2.20 mol of phenol used in Synthesis Example 15 was added to 2
-The same operation as in Synthesis Example 15 was carried out except that sodium salts of 2-allylphenol, N-propanol and 4-cyanophenol were prepared with metallic sodium, instead of 2.00 mol of allylphenol and 0.20 mol of N-propanol. A phosphazene compound having a 4-cyanophenoxy group was synthesized. Table 5 shows the results. Elemental analysis of carbon, hydrogen, nitrogen, chlorine and phosphorus of this product and ¹ H-NM
From the measurement results of the R and ³¹ P-NMR spectra, it was confirmed that the composition of the product coincided with the charging ratio of 4-cyanophenol, 2-allylphenol and N-propanol, and that the target product could be synthesized.

Synthesis Example 25 Hexachlorocyclotriphosphazene 1.5 mol (5
21.6 g) was heated to 250 ° C. for 12 hours under a nitrogen atmosphere, and a dichlorophosphazene polymer was obtained by ring-opening polymerization. Unreacted hexachlorocyclotriphosphazene was removed by sublimation at 70 ° C. under reduced pressure for 7 hours. 224.3 g of the obtained dichlorophosphazene polymer (yield: 43
%) With chlorobenzene to give a 20% solution. In the same manner as in Synthesis Example 15, a toluene solution of cyanophenol and a sodium salt of phenol was prepared.

580 g of a 20% chlorobenzene solution in which 1 unit mol (115.9 g) of the dichlorophosphazene polymer prepared above was dissolved was added dropwise to this toluene solution of the sodium salt of phenol at 30 ° C. or lower while stirring. This mixture was refluxed for 12 hours. The reaction mixture was concentrated and reprecipitated in a 5% aqueous sodium hydroxide solution. Next, the precipitated polymer was dissolved in tetrahydrofuran and reprecipitated in water. This operation was performed three times. Vacuum drying of the produced polymer (vacuum drying conditions: 80 ° C, 5 mmH
g, 12 hours) to obtain 213 g of a slightly yellow viscous liquid. Table 5 shows the results. The carbon, hydrogen,
Elemental analysis, ¹ H-NMR and ³¹ P of nitrogen, chlorine and phosphorus
According to the measurement result of the NMR spectrum, the composition of the product was 4
-Matches the charge ratio of cyanophenol to phenol,
It was confirmed that the target compound was synthesized.

[0219]

[Table 5]

Examples 38 to 48 75 parts of aromatic polycarbonate resin and 25 parts of ABS resin
Of a phosphazene compound having a cyanophenoxy group synthesized in Synthesis Examples 15 to 25, and mixed with a mixer, followed by melt-kneading using a Labo Plastomill to obtain a flame-retardant resin composition. Was.

A test piece having a predetermined shape was prepared from this composition by a heat press, and a combustion test, an Izod impact strength and a heat distortion temperature based on the UL-94 test method were measured according to the following methods. went. Table 6 shows the results. -Combustion test It was performed according to the UL-94 specified vertical combustion test method and used as an index of flame retardancy. (Test piece: thickness 1/16 inch, length 5 inch, width 0.5 inch) Izod impact strength Measured at 23 ° C. according to JIS K-7110, and used as an index of impact resistance. (Specimen thickness 1/8 inch, with V notch) ・ Heat deformation temperature Load 18.6k by the method based on ASTM D-648
g / cm ^2, which was used as an index of heat resistance.

Comparative Example 12 Table 6 shows the results of preparation and evaluation of a sample in the same manner as in Example 38 except that triphenyl phosphate was used in place of the phosphazene compound used in Example 38.

Comparative Example 13 In place of the phosphazene compound used in Example 38, a condensed phosphoric acid diphenyl ester cross-linked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.) was used. Table 6 shows the results of sample preparation and evaluation.

Comparative Example 14 Table 6 shows the results of sample preparation and evaluation conducted in the same manner as in Example 38, except that no flame retardant was added.

Example 49 A sample was prepared by adding 0.5 parts of zinc chloride in the formulation of Example 38, and the flame retardancy and the heat distortion temperature were evaluated.
Table 6 shows the results.

Example 50 In the composition of Example 38, commercially available polytetrafluoroethylene (trade name: F-201, manufactured by Daikin Industries, Ltd.)
Was added to prepare a sample, and the flame retardancy and the heat distortion temperature were evaluated. Table 6 shows the results.

Examples 51 to 55 A cyanophenoxy group synthesized in Synthesis Examples 15 to 19 was added to a resin composed of 70 parts of poly (2,6-dimethyl-1,4-phenylene) oxide and 30 parts of rubber-modified impact-resistant polystyrene. Was added and mixed with a mixer, followed by melt-kneading using a Labo Plastomill to obtain a flame-retardant resin composition. The combustion test based on the UL-94 test method, the measurement of the Izod impact strength and the measurement of the heat distortion temperature were performed according to the methods described above. Table 6 shows these results.
Shown in

Comparative Example 15 A sample was prepared and evaluated in the same manner as in Example 51, except that triphenyl phosphate was used in place of the phosphazene compound used in Example 51. Table 6 shows the results.

Comparative Example 16 In place of the phosphazene compound used in Example 51, a condensed phosphoric acid diphenyl ester cross-linked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.) was used. Table 6 shows the results of sample preparation and evaluation.

Comparative Example 17 A sample was prepared and evaluated in the same manner as in Example 51, except that no flame retardant was added. Table 6 shows the results.

Example 56 Nylon 610 having a number average molecular weight of 25,000
To 0 parts, 10 parts of the phosphazene compound having a cyanophenoxy group synthesized in Synthesis Example 15 was added, mixed with a mixer, and then melt-kneaded using a Labo Plastomill to obtain a flame-retardant resin composition.

A sample piece was prepared in the same manner as in Example 38,
A combustion test based on the UL-94 test method, and measurement of Izod impact strength and heat distortion temperature were performed. Table 6 shows the results.

Comparative Example 18 In place of the phosphazene compound used in Example 56, a condensed phosphoric acid diphenyl ester cross-linked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.) was used. Table 6 shows the results of sample preparation and evaluation.

Example 57 70 parts of a polycarbonate resin, 30 parts of a polybutylene terephthalate resin, and 20 parts of a phosphazene compound having a cyanophenoxy group synthesized in Synthesis Example 15 were mixed by a mixer, and then melt-kneaded using a Labo Plastomill. A flammable resin composition was obtained.

A sample was prepared in the same manner as in Example 38.
A combustion test based on the UL-94 test method, and measurement of Izod impact strength and heat distortion temperature were performed. Table 6 shows the results.

Comparative Example 19 A diphosphoric acid diphenyl ester cross-linked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.) was used in place of the phosphazene compound used in Example 57. Table 6 shows the results of sample preparation and evaluation.

Example 58 A varnish was prepared by adding 10 parts of the phosphazene compound having a cyanophenoxy group synthesized in Synthesis Example 15 to 100 parts of a bisphenol-A type epoxy resin, and a varnish was impregnated with glass cloth and dried. Thus, a prepreg was prepared. Subsequently, a predetermined number of prepregs were stacked and heated and pressed at 160 ° C. or more to produce glass epoxy plates having a thickness of 1/8 and 1/16 inch, and cut into prescribed dimensions to obtain test pieces.

Using this test piece, a combustion test based on the UL-94 test method, and measurement of Izod impact strength and heat distortion temperature were carried out in accordance with the above-mentioned methods. Table 6 shows the results. No juicing was observed during hot pressing.

Example 59 A sample was prepared in the same manner as in Example 58 except that the compound synthesized in Synthesis Example 23 was used instead of the phosphazene compound having a cyanophenoxy group (compound synthesized in Synthesis Example 15) used in Example 58. Table 6 shows the results of fabrication and evaluation. No juicing was observed during hot pressing.

Comparative Example 20 Instead of the phosphazene compound synthesized in Synthesis Example 15, diphenyl condensed phosphate crosslinked with resorcinol (a compound similar to CR733S manufactured by Daihachi Chemical Industry Co., Ltd.)
Table 6 shows the results of sample preparation and evaluation performed in the same manner as in Example 58 using Juicing was observed during hot pressing.

Comparative Example 21 Table 6 shows the results of sample preparation and evaluation performed in the same manner as in Example 58, except that no flame retardant was added.

[0242]

[Table 6]

Table 6 shows that the resin composition of the present invention has excellent balance of flame retardancy, impact resistance and heat resistance by optimizing and blending each resin and phosphazene. (Example 38)
~ 59). Further, in Example 49, by adding a small amount of zinc chloride to a mixed resin of an aromatic polycarbonate resin, an ABS resin and a phosphazene compound having a cyanophenoxy group, more excellent flame retardancy and impact resistance were exhibited. I understand. On the other hand, when a phosphate ester compound is used as a flame retardant, flame retardancy and heat resistance are poor,
It can be seen that the practical utility value is low (Comparative Examples 12 to 1).
3, 15-16, 18-20).

Example 60 Aromatic polycarbonate resin (trade name: Iupilon S-
2000N, 100 parts of a resin composition composed of 75 parts of Mitsubishi Engineering-Plastics Co., Ltd.) and 25 parts of ABS resin (trade name: Santac UT-61, manufactured by Mitsui Chemicals, Inc.), triphenyl phosphate (Wako Pure Chemical Industries, Ltd.) 5.0 parts of fexophosphazene synthesized in Synthesis Example 14 and 0.6 parts of polytetrafluoroethylene (trade name: G-307, manufactured by Asahi Glass Co., Ltd.) are twin-screw extruders. , And pelletized to produce pellets of the flame-retardant resin composition of the present invention.

Comparative Examples 22 and 23 In Example 60, except that triphenyl phosphate and phenoxyphosphazene were not used together and 10 parts of triphenyl phosphate alone (Comparative Example 22) or 10 parts of phenoxyphosphazene alone (Comparative Example 23) were used. In the same manner as in Example 60, pellets of the resin composition were produced.

Examples 61 to 63 In Example 60, triphenylphosphine oxide (manufactured by Kanto Chemical Co., Ltd., Example 6) was used in place of triphenyl phosphate as the halogen-free organic phosphorus compound.
1), tricresyl phosphate (manufactured by Wako Pure Chemical Industries, Ltd.,
Pellets of the flame-retardant resin composition of the present invention were produced in the same manner as in Example 60 except that Example 62) or resorcinol bis (2,6-dimethylphenyl phosphate) (Example 63) was used.

Comparative Examples 24 to 26 In Examples 61 to 63, a halogen-free organic phosphorus compound and phenoxyphosphazene were not used together, and only triphenylphosphine oxide (Comparative Example 24), tricresyl phosphate alone (Comparative Example 25) or Resorcinol bis (2,6-dimethylphenyl phosphate)
Examples 61 to 60 except that 10 parts of (Comparative Example 26) were used.
Similarly to 63, pellets of the resin composition were produced.

Example 64 A pellet of the flame-retardant resin composition of the present invention was prepared in the same manner as in Example 60 except that the phosphazene compound synthesized in Synthesis Example 3 was used instead of phenoxyphosphazene. Manufactured.

Example 65 Pellets of the flame-retardant resin composition of the present invention were prepared in the same manner as in Example 60 except that the phosphazene compound synthesized in Synthesis Example 4 was used instead of phenoxyphosphazene. Manufactured.

Example 66 Example 60 was repeated except that a modified PPE resin (trade name: Xylon X9108, manufactured by Asahi Kasei Kogyo KK) was used instead of the mixed resin of the polycarbonate resin and the ABS resin. Similarly, pellets of the flame-retardant resin composition of the present invention were produced.

The resins, halogen-free organic phosphorus compounds and phosphazene compounds in Examples 60 to 66 and Comparative Examples 22 to 26 are summarized in Table 7 below. The amount in parentheses is the amount (parts).

[0252]

[Table 7]

PC: aromatic polycarbonate resin (trade name: Iupilon S-2000N, manufactured by Mitsubishi Engineering-Plastics Corporation) ABS: ABS resin (trade name: Santac UT-61,
TPP: triphenyl phosphate (Wako Pure Chemical Industries, Ltd.)
TPPO: Triphenylphosphine oxide (Kanto Chemical Co., Ltd.) TCP: Tricresyl phosphate (Wako Pure Chemical Industries, Ltd.)
LBDP: resorcinol bis (2,6-dimethylphenyl phosphate) Pellets of the resin compositions obtained in Examples 60 to 66 and Comparative Examples 22 to 26 were injection-formed to prepare test pieces of a predetermined shape. A combustion test based on the UL-94 test method, a flexural modulus, a heat distortion temperature, an Izod impact strength and a melt flow rate were measured. The combustion test, the measurement of the heat distortion temperature and the measurement of the Izod impact strength were performed according to the methods described above. The measurement of the flexural modulus and the melt flow rate was performed according to the method shown below. -Flexural modulus Measured by a method according to JIS-K7203.・ Melt flow rate According to JIS-K7210, 10 ° C at 240 ° C
The measurement was performed with a load of kg.

The results are shown in Table 8 below.

Example 67 Bisphenol-A type epoxy resin (trade name: EP54)
00, manufactured by Asahi Denka Kogyo Co., Ltd.), 100 parts of triphenyl phosphate, 7.5 parts of phenoxyphosphazene synthesized in Synthesis Example 14, and 0.6 part of polytetrafluoroethylene (G-307) were mixed. A varnish of the flame-retardant resin composition of the present invention was produced.

The varnish was impregnated in a glass cloth and dried to obtain a prepreg. Five prepregs were stacked and pressed at 160 ° C. at 50 kg / cm ² to produce a 1.6 mm thick glass epoxy plate. And length 12.7
cm and a width of 1.3 cm to prepare a test piece. This test piece was subjected to each of the tests described above. Table 8 shows the results.

[0257]

[Table 8]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09K 21/14 C09K 21/14 (72) Inventor Yuji Tada 463 Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Pref. (72) Inventor Yoichi Nishioka 463 Kagasuno, Kawauchi-cho, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd. CC101 CC181 CC211 CD001 CF001 CF061 CF071 CG001 CH071 CH091 CK021 CL001 CM021 CM041 CM051 CN011 CN031 CQ012 EW156 FD132 FD136 GC00 GQ00 4J030 CB42 CB48 CG21 CG22

Claims (4)

[Claims] 1. A compound of the general formula (3)[Wherein m represents an integer of 3 to 25. R¹Is the cyano substitution
Represents a phenyl group. R^TwoIs an alkyl group having 1 to 18 carbon atoms,
GroupOr groupIs shown. Where R^ThreeRepresents a hydrogen atom, a cyano group, and a carbon number of 1 to
And 10 alkyl groups, allyl groups or phenyl groups. R
^TwoWhen there are two or more^TwoMay be the same
And may be different. p and q are p> 0, q ≧ 0
Is a real number satisfying p + q = 2. ]
Cyclic phosphazene compound represented by general formula (4):[Where R¹, R^Two, P and q are the same as above. n is 3 to 10
Indicates an integer of 00. X 'is a group -P (OR¹)_Four, Group -P
(OR¹)_Three(OR^Two) Group, -P (OR¹)_Two(OR^Two) _Two,
Group-P (OR¹) (OR^Two)_Three, Group -P (OR^Two)_Four, Group-
P (O) (OR¹)_Two, Group -P (O) (OR¹) (OR^Two)
Or a group -P (O) (OR^Two)_TwoAnd Y 'represents a group -N = P
(OR¹)_Three, Group -N = P (OR¹)_Two(OR^Two), Group -N
= P (OR¹) (OR^Two)_Two, Group -N = P (OR^Two)_Three, Basis
-N = P (O) OR¹Or a group -N = P (O) OR^TwoIndicates
You. A group consisting of the linear phosphazene compounds represented by the formula:
From at least one phosphazene compound selected from
Become a flame retardant. 2. The phosphazene compound, wherein R ¹ is a cyano-substituted phenyl group, R ² is an alkyl group having 1 to 8 carbon atoms, and a group represented by the following formula: Or group R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an allyl group, p is 0.3 to 1.7, and q is 0.3 to
A cyclic phosphazene compound of the general formula (3) wherein R ¹ is a cyano-substituted phenyl group; R ² is an alkyl group having 1 to 8 carbon atoms; Or group R ³ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an allyl group, p is 0.3 to 1.7, and q is 0.3 to
2. At least one member selected from the group consisting of linear phosphazene compounds of the general formula (4) having a ratio of 0.7.
The flame retardant according to the above. 3. A flame-retardant resin composition comprising 0.1 to 100 parts by weight of the phosphazene compound according to claim 1 or 2 with respect to 100 parts by weight of a thermoplastic resin or a thermosetting resin. object. 4. A flame-retardant resin molded article obtainable by molding the flame-retardant resin composition according to claim 3.